Process for preparing polymeric sulfides



United States Patent 3,326,977 PROCESS FOR PREPARING POLYMERIC SULFIDESDee L. Johnson and Delbert D. Reynolds, Rochester,

N. Y., assignors to Eastman Kodak Company, Rochester, N.Y., acorporation of New Jersey No Drawing. Filed Jan. 12, 1962, Ser. No.165,931 9 Claims. (Cl. 260-584) This application is acontinuation-in-part of the copending Johnson and Reynolds US. patentapplication Serial No. 80,970, filed January 6, 1961, now abandoned.

This invention concerns a process for preparing polymeric sulfides and,more particularly, polymers in which the repeating unit is a derivativeof ethylene sulfide. These polymers will hereinafter be referred to asoligoethylene sulfides.

In Reynolds US. patent application Serial No. 721,678, filed March 17,1958, it is shown that introduction of a mercaptoethyl group into asubstance such as an amine or mercaptan yields a nonpolymericmercaptoethyl derivative. The reaction described therein was' carriedout in a solvent medium such as toluene or dioxane, which medium isnonpolar or very slightly polar.

It is the object of our invention to produce polymeric sulfides. Afurther object is to introduce into organic substances more than onemercaptoethyl group such that oligoethylene sulfides are obtained.

These objects are accomplished byv a process for preparing polymericsulfides of the general formula where r may be 1 or 2, R'- may behydrogen, hydroxymethyl, or alkyl (C -C n is an integer from 2 to 20,

and X is (a) i i G C O)m m being 0 to l, where r is l, G may be RHN-,RRN, and ZN, where R is alkyl (C -C cycloalkyl, aralkyl, or aryl and Zmay be 4 or 5 carbon or oxygen atoms necessary to complete aheterocyclic ring with N, and when r is 2, G may be' or RRNN=, where Yis hydrogen or R (defined above) and x is 2 to 18; (b) H N; (0) HO; (d)RS (R defined above); and (e) RO- (R defined above); comprising reactingQCO-ACH -CHR'BH, where Q is an alkoxy group of 1 to 18 carbon atoms, or,together With the hydrogen atom of B (i.e. to form QH), is a covalentbond forming a heterocyclic ring; R is defined as above; and A and B aredissimilar and may be selected from the class consisting of sulfur andoxygen; with a nucleophilic initiating agent chosen from the groupconsisting of (l) XH, Where X is G (defined above), Na0, KO, and NH O,and (2) XM, where X is RO and RS (R defined above) and M is an alkalimetal, in a mercaptide ion-enhancing medium.

The bringing together of the reactants of our process in a medium whichenhances or promotes the formation of mercaptide ions is critical forthe performance of our invention to produce oligoethylene sulfides. Ifthe reactants are placed in a medium which inhibits the formation ofmercaptide ions, such as the media found in Reynolds, application SerialNo. 721,678 (now abandoned), mentioned above, then the desiredpolymerization process does not occur.

The mercaptide ion-enhancing medium is most easily obtained by placingthe process reactants in a solvent which induces ionization. Suchsolvents include alcohols, water, acetonitrile, propionitrile,dialkylformamides, and

3,326,977 Patented June 20, 1967 the like. In general solventsconsidered polar solvents are operable. It will be readily apparent thatin many instances the desired mediumis obtained from one of the processreactants. For example, when the process reactant is itself an alcohol,a mercaptan, or a strongly basic amine, such as aliphatic amines orhydrazines, then additional solvent is optional and may even be anonpolar or weakly-polar one. For certain process reactants such asweakly-basic amines, e.g. aromatic amines, the mercaptide ion formationis induced by the addition to the reaction mass of an alkali metalalkoxide, for example sodium methoxide. In any of above-mentionedroutes, the necessary mercaptide ion-promotion medium is established forthe reactants and the desired polymerization process is operabletherein.

One of the reactants necessary for operating our process is Q-COA-CH-CHR'--BH in which Q is an alkoxy group of l to 18 carbon atoms, or,together with the hydrogen atom of B (i.e. to form QH), is a covalentbond forming a heterocyclic ring; R is hydrogen, hydroxymethyl or alkyl(C -C and A and B are dissimilar and may be selected from the classconsisting of sulfur and oxygen. Representative compounds which we finduseful include ethylene monothiolcarbonate,

II 0 substituted ethylene monothiolcarbonates, alkyl 2-hy-'droxyalkylthiolcarbonates, and alkyl 2-mercaptoethyl-carphase solventsystem is used employing water and an immiscible inactive solvent, suchas benzene, petroleum ether, or the like. The alkyl2-mercaptoethylcarbonates are prepared by isomerizing the correspondingalkyl 2- hydroxyethylthiolcarbonates. For example, n-hexyl 2-mercaptoethylcarbonate may be prepared in a 200-ml. flask equipped witha 14-inch packed column, and a variable-rate still-head. In the flask isplaced 103 grams (0.5 mole) of n-hexyl 2-hydroxyethylthiolcarbonate and0.002 gram of uranyl acetate. The system is placed under vacuum anddistilled, producing 85 grams or 82 percent yield of n-hexylZ-mercaptoethylcarbonate (boiling point /0.2 mm., refractive index1.4542, 99.5 percent pure by iodometric titration). Similarly treating2-mercapto-l,3- propanediol or'2- mercapto-l-alkanols with an alkylchloroformate yields alkyl lhydroxymethyl 2 hydroxyethylthiolcarbonateor alkyl l-alkyl 2 hydroxyethylthiolcarbonate, which on isomerizationyield, respectively, alkyl 2-hydroxymethyl 2 mercaptoethylcarbonate andalkyl 2-alkyl-2-mercaptoethylcarbonates. Ethylene monothiolcarbonate maybe prepared from phosgene and 2- mercaptoethanol as described in US.Patent No. 2,828,- 318 (Reynolds) which issued March 25, 1958. Similarlyhydroxyrnethyl and alkyl substituted ethylene monothiolcarbonates may beobtained by replacing Z-mercaptoethanol with the appropriatelysubstituted 2-n1ercaptoethanolic compound. The preferred members of theQ-COACH CHR'-BH family are ethyl 2-mercaptoethylcarbonate, ethylenemonothiolcarbonate, and ethyl 2-hydroxyethylthiolcarbonate.

The other reactant of our process is a nucleophilic initiating agentchosen from the group consisting of (l) XH, where X is G- (definedabove), NaO-, KO-, and NH O, and (2) XM, Where X is RO and RS (Rdefinedabove) and M is an alkali metal. Representative examples ofnucleophilic initiating agents which are perable in our process includeprimary and secondary aliphatic, alicyclic, aromatic, aralkyl andheterocyclic amines; primary and secondary aliphatic and heterocyclicdiamines; aliphatic and aromatic hydrazines; sodium hydroxide; potassiumhydroxide; ammonium hydroxide; the sodium, potassium, or lithium saltsof alkanols, cycloalkanols, aralkanols, phenols and the like; and thesodium, potassium, or lithium salts of mercaptans such as alkauethiols,cycloalkanethiols, aralkanethiols, thiophenols, and the like. When thenucleophilic initiating agent contains more than one functional group asin alkanolamines,

mercaptoalkanols, and the like, the hydroxyl group being the leaststrong initiator is to be considered for the purposes of our inventiononly a substituent of the amine, mercaptan, and the like. In certaininstances it will be convenient to prepare the nucleophilic initiatingagent in situ by adding convenient precursors to the reaction vessel.For example, ammonia and water may be used for in sit-u ammoniumhydroxide. Similarly free alcohol or mercaptan and alkali metal oralkali metal alkoxide may be added as a pair to obtain'the ROM or RSM insitu. Our preferred nucleopholic initiating agents include ethonolamine,N-methylethanolamine, diethanolamine, 2-amino- 2-methyl-l-propano-l,2-a-mino-2-rnethyl-l,3 propanediol, 2-amino 2 (hydroxymethyl) 1,3propanediol, ndecylamine, cyclohexylamine, morpholine, ethylamine,diethylamine, benzylamine, aniline, a,a,a-trifluorotoluidine,ethylenediamine, piperazine, N,N-dimethylhydrazine, sodium hydroxide,ethanol (as the alkoxide), benzyl alcohol (as the alkoxide),l-butanethiol (as the alkali metal mercaptide), p-thiocresol (as thealkali metal mercaptide), and 3mercapto'-1,2 propanediol (as the alkalimetal mercaptide).

In general the process for preparing oligoethylene sulfides isconveniently simple. The reactants with or without additional solvent,as needed to produce the mercaptide ion-promoting medium, are mixed in avessel at room temperature and the nucleophilic initiating agent inducespractically instantaneous reaction. To achieve highest yields ofpolymer, one may optionally heat at reflux temperature of any liquidpresent in the reaction vessel for a short period, say one to two hours.Any remaining extraneous liquids, such as original solvent or unchangedstarting reactant, may be removed by distillation at reduced pressures,the desired polymer remaining. In many instances, the molecular weightof the polymer is such that the desired polymeric product precipitatesfrom the reaction medium and may be separated by simple filtration.

In certain instances the structure of the desired polymeric product caninfluence the choice of reaction conditions. When the nucleophilic agentis an unhindered amine, for example n-butylamine, an intermediate 2-mercaptoethyl N-n-butylcarbamate forms rapidly and in temporary excess,in the reaction with ethylene monothiolcarbonate. This intermediate isstrongly nucleophilic and, being present in an excess, leads to theoligoethylene sulfide (i.e.v in general. formula 111:1). When the amineis hindered, for example tert.- butylamine, the intermediate,Z-mercaptoethyl N-tert.- butylcarbamate, is not formed rapidly and inexcess, and

the original hindered amine remains the nucleophilic agent producing theoligoethylene sulfide tert.

C H NH (CI-I CH H (i.e. in general formula m=0). To obtainaminooligoethylene sulfide (i.e. m=0) from an unhindered amine liken-butylamine, the amine nucleophilic initiating agent must be kept inexcess by the simple expediency of placing it in the reaction vesselfirst and slowly adding ethyl 2-mercaptoethylcarbonate to obtain n-C HNH(SH CH S) ,H (i.e.

The oligoethylene sulfides prepared by the process of our invention areuseful silver complexing agents and can be used in various photographicsystems. In electrophotography, these polymers are especially Valuableas constituents in electrolytic developing solutions. for singlestepdirect image-forming photoconductographic processing as described in D.L. Johnson et al., US. Serial No. 117,125, filed June 14, 1961, now US.Patent No. 3,072,542. In silver halide photographic systems they areuseful as fixers or stabilizers. In silver halide diffusion transferprocessing they improve the tone of silver images.

The following examples are intended to illustrate our invention but notto limit it in any way.

Example 1.1,1 dimethyl 2 hydraxyethylaminooligo ethylenesulfide One mole(89 g.) of 2-amino-2-methyl-l-propanol was dissolved in 1 liter ofdioxane brought to reflux under an effective condenser as 1 mole (150g.) of ethyl-2- mercaptoethylcarbonate was added dropwise in 1.5 hours.The mixture was refluxed 0.5 hour, then stripped of solvent and someexcess amine. The product (99 g.) was the residue in the flask with anaverage molecular weight (by I titration) of 263 or 2.9 repeatingethylene sulfide units.

Example 2.1,1(dihydr0xymethyl) ethylaminooligoethylenesulfide To asolution of 1 mole g.) 2-amino-2-methyl- 1,3-propanediol in 1 liter ofdiOXane at reflux under an eifective condenser was added 1 mole g.)ethyl-2- mercaptoethylcarbonate dropwise in 1.5 hour- The mixture wasrefluxed an additional 0.5 hour then stripped of solvent under aspiratorvacuum. The product was the residue in the flask with a molecular weightof 311 or 3.43 repeating ethylene sulfide units.

Example 3 .Tris-(hydr0xymethyl methylaminooligoethylenesulfide To arefluxing solution of 121 :g. (1 mole) 2-amino-2-hydroxymethyl-1,3-propanediol' and 500 ml. dioxane-SOO rnl.tetrahydrofurfuryl alcohol was added 150 g. (1 mole) ethylZ-mercaptoethylcarbonate dropwise in 1 hour. The reaction mixture wasrefluxed 1 hour additional and stripped of solvent. The product was theresidue in the flask, 174 g. with a molecular weight 293. or 4.88repeating ethylene sulfideunits.

Example 4.2-hydr0xyethylamino-oligoethylene sulfide Three moles g.)2-arninoethanol were dissolved in 1.4 liter of toluene and 800 ml. ofdioxane and brought to reflux under an efficient condenser. To thissolution was added 1 mole (150 g.) of ethyl Z-mercaptoethylcarbonatedropwise in 2.5 hours. After addition the mixture was refluxed 2 hours.The solvent and excess amine were stripped by vacuum distillationleaving 104 g. of a viscous oil N 1.5338. By iodometric titration theproduct had an average molecular weight of 142 which indicates anaverage of 1.35 repeating ethylene sulfide units. The calc. value forC2H7NO(C2H4S)1 35 is C, 39.4; H, 8.7; N, 9.9; S, 30.4. Found: C, 39.6;H, 8.8; N, 9.9; S, 29.9.

Example 5 .n-Butylamino-oligoe-thylene sulfide To a refluxing solutionof g. (0.2 mole) n-butylamine 30 ml. water and 200 ml. methanol wasadded dropwise in 30 minutes. 30 g. (0.2 mole) ethylZ-mercaptoethylcarbonate. Refluxed 1 hour duringwhich time the alcoholwas boiled 01f. Cold water was added and the white powder was collectedhaving a molecular weight of 690 or 10.4 repeating ethylene sulfideunits.

Example 6.-n-Decylamino-oligoethyIene sulfide Sixteen grams (0.1 mole)n-decylamine, 100 ml. methanol and 100 ml. water were refluxed on asteam bath while 30 g. (0.2 mole) ethyl Z-mercaptoethylcarbonate wasadded dropwise in 30 minutes. After refluxing an additional hour thewhite solid was collected after adding ice and washed with ethanolyielding 13 g. of product with a molecular weight of 1214 or 17.2repeating ethylene sulfide units.

Example 7 .Amino-oligoethylene sulfide Ethyl Z-mercaptoethyl carbonate,60 g. (0.4 mole) was added dropwise in 30 minutes to 250 ml.concentrated ammonium hydroxide at 40. After the addition was complete250 ml. concentrated ammonium hydroxide was add: ed and the thickmixture was heated 15 min. on a steam bath. The white product wascollected by vacuum filtration, washed with cold water to yield a powderwith a molecular weight of 471 or 7.6 repeating ethylene sulfide units.

Example 8.Bis(2-hydr0xyethyl) amino-oligoethylene sulfide To avigorously refluxing mixture of 105 g. (1 mole) 2,2-iminodiethanol and0.5 liter dioxane under an effective condenser was added 150 g. (1.0mole) ethyl Z-mercaptoethylcarbonate dropwise in 1 hour. The reactionwas refluxed 1 hour, stripped of solvent leaving 120 g. of producthaving a molecular weight of 347 or 5.79 repeating ethylene sulfideunits.

Dimethylamino-oligoethylene sulfide Twenty two grams (0.5 mole) dimethylamine were dissolved in 500 ml. water, warmed on a steam bath to whichwas added 150 g. (1.0 mole) ethyl 2-mercaptoethyl carbonate dropwise in1 hour with an additional 2 hour reflux. The white powdery 'product hada molecular weight of 495 or 7.5 repeating ethylene sulfide units.

Di-n-dodecylamino-oligoethylene sulfide To a refluxing solution of 35.3g. (0.1 mole) di-ndodecylamine and 500 ml. methanol was added 75 g. (0.5mole) ethyl 2-mercaptoethylcarbonate dropwise in 30 minutes. Afterrefluxing overnight a soft solid product was obtained with a molecularweight of 679 or 5.43 repeating ethylene sulfide units,

Example 9.--Benzylamino-oligoethylene sulfide Example10.N-methylberzzylamino-oligoethylene sulfide To a refluxing solution of30 g. (.25 mole) N-methylbenzylamine, 250 ml. water, and 250 m1.methanol was added 150 g. (1.0 mole) ethyl Z-mercaptoethylcarbonatedropwise in 1 hour. The mixture was refluxed 2 hours more and the whitesoli-d collected had a molecular weight of 456 or 5.58 repeatingethylene sulfide units.

Example 11 -Ethyl mereapto-oligoethylene sulfide Example12.-Mercapto-0lig0ethylene sulfide Hydrogen sulfide was passed into 500ml. of heated (steam bath) concentrated ammonium hydroxide solution for30 min. To this was added 150 g. (1 mole) ethyl Z-mercaptoethylcarbonatedropwise in 30 min. The

' mixture was then refluxed overnight and a white polymeric powdercollected with a molecular weight of 531 or 8.3 repeating ethylenesulfide units.

Example 13.-Benzylmercapto-oligoethylene sulfide To a solution of 30 g.(0.25 mole) of benzenemethanethiol 11 g. (0.25 mole) sodium methoxideand 300 ml. N-methylpyrrolidone heated on a steam bath was added 225 g.(1.5 mole) ethyl Z-mercaptoethylcarbbnate dropwise in 3 hours. A clearsolution resulted which upon cooling precipitated 98 g. of white solidwhich was triturated with ether. The solid has a molecular weight of1200 or 18 repeating ethylene sulfide units.

' Example 14.N-ethylanilino-oligoethylene sulfide Example 15 .2-(ethoxyethoxy -eth0xy-0lig0ethylene sulfide Six grams (0.3 mole) sodiumwas added to 500 ml. 2-(ethoxyethoxy)-ethanol and heated on a steambath. To this solution was added 150 g. (1.0 mole) ethyl2-mercaptoethylcarbonate dropwise in 1 hour. Subsequently the reactionwas refluxed 1 hour. The white precipitate was collected by vacuumfiltration triturated with ether yielding 60 g. with a molecular weightof 1109 or 16.3 repeating ethylene sulfide units.

Example 16.Eth0xy0lig0ethylene sulfide Six grams (0.3 mole) sodium wasdissolved in 175 ml. ethanol brought to reflux and 36 g. (0.24 mole)ethyl 2- mercaptoethylcarbonate added dropwise in 30 min. After anadditional 30 min. reflux the white polymeric powder was collected,triturated in ether and had a molecular weight of 440 or 5.57 repeatingethylene sulfide units.

7 Example 17.Benzyloxyoligoethylenesulfide 'A solution of 6 g. (0.3mole) sodium and 500 ml. benzyl alcohol was heated on a steam bath whileg. (1.0 mole) ethyl 2-mercaptoethylcarbonate was added dropwise in 1hour. The mixture was refluxed overnight and upon cooling a soft solidwith a molecular weight of 763 or 10.9 repeating ethylene sulfide unitswas collected. v

Example 18.-Hydr0xy-0ligoethylene sulfide The dropwise addition of 37.5g. (0.25 mole) ethyl 2- mercaptoethylcarbonate in 30 min. to a solutionof 10 g. (0.25 mole) sodium hydroxide :and 300 ml. water heated on asteam bath quickly formed a white solid. After an additional 30 min.reflux the solid was collected and found to have a molecular weight of346 or 5.5 repeating ethylene sulfide units.

Example 19.Phen'xy-0ligoethylene sulfide To a solution of 219 g. phenoland 16 g. (0.25 mole) sodium methoxide heated on a steam bath was addeddropwise in minutes, 75 g. (0.5 mole) ethyl Z-mercaptoethylcarbonate.The white mass liquified and was refluxed 1 hr. and while hot filtered,triturated with 100 ml. ether, then 100 ml. acetone to give 23 g. ofwhite powder with a molecular weight of 1192 or 18.3 repeating ethylenesulfide units.

Example 20.N-butylamino-oligoethylene sulfide Fifteen grams (0.2 mole)n-butylamine, 250 ml. methanol, and 250 ml. water were refluxed on asteam bath. To this solution was added 30 g. (0.2 mole) ethyl2-hydroxyethylthiolcarbonate dropwise in 20 min. The refluxing wascontinued 45 min. as the white solid precipitated from solution, wassubsequently collected, triturated in water and when dry 12.5 g. had amolecular weight of 740 or 11.1 repeating ethylene sulfide units.

Example 21 .Benzylmercapto aligoethylene sulfide Ethyl2-hydroxyethylthiolcarbonate (150 g., 1.0 mole) was added dropwise in 30min. to :a refluxing solution of 30 g. (0.2 mole) benzenemethanethioland 11 g. (0.2

, mole) sodium methoxide in 250 ml. each of methanol and Example23.-n-Butylcarbamolylaxy-oligoethy[ene sulfide One-half mole of ethylenemonothiolcarbonate and 1.5 mole ofn-butylamine was refluxed in a mixtureof 500 ml. of methanol and 500 ml. of water. After 6 hours the solid wasseparated and dried. Iodometric titration gave an apparent molecularweight of 42.2. A strong carbonyl was shown at 5.96 microns. These dataalong with elemental analysis indicated its structure as Example24.-ls0pr0pylcarbamoylaxy-aligoezhylene sulfide andisopropylamina-oligaethylene sulfide One-half mole of ethylenemonothiolcarbonate and 1.5 mole of isopropylamine were refluxed togetherfor six hours in a mixture of 500 ml. of methanol and 500 ml. of water.The dried oligomer had an apparent molecular weight of 540. Infrared andelemental analysis indicated that it was a mixture of the oligomers,

(CH CHNHCO CH CH S) H and (CH CHNH (CH CH S H Example 25.tert.Butylamino-o ligoethylene sulfide One-half mole of ethylenemonothiolcarbonate and 1.5 moles'of tert.butylamine were refluxedtogether in a mixture of 500 ml. of methanol and 500 ml. of water. Thedried, white oligomer showed an apparent molecular weight of 503. Itsinfrared showed no carbonyl band. These data along with elementalanalysis indicated the structure tert. 7H.

Analysis.Calcd. for above structure: C, 43.8; H, 7.9; N, 2.8; S, 45.4.Found: C, 43.4; H, 7.9; N, 2.5; S, 45.1.

Example 26.Carbamoyloxy-aligoethylene sulfide One-half mole of ethylenemonothiolcarbonate was stir-red into a mixture of 200 ml. of 28% NH OHand 200 ml. of water. A white oligomer separated within a few minutes.The washed and dried product gave a molecular Weight of 297.

In a second experiment the ethylene monothiolcarbonate was addeddropwise over a 45 minute period. The apparent molecular weight was 156.The infrared curves were identical for both products and indicated thestructure to 'be H NCO (CH CH S) I-I.

Example 27.-n-0ctylcarbam0yloxy oligoethylene sulfide One-tenth mole ofethylene monothiolcarbonate and 0.1 mole of n-octylamine refluxedtogether for 5 hours in a mixture of 75 ml. of methanol and 75 ml. ofwater. The polymer was washed and dried. The infrared exhibited a verystrong carbonyl indicating the structure to be n-C H NHCO (CH CH S) ,H.

Example 28.--Benzylcarbam0yl0xy-olig0ethylene sulfide Example 27 Wasrepeated in which the n-octylamine was replaced by benzylamine. Infraredanalysis indicated the structure to be C H CH NHCO (CH CH S),,H. It hada molecular weight of 381. An-oligomer of the same structure wasobtained when the ethylene monothiolcarbonate was added dropwise over a60 minute period.

Example 29.N-methylbenzylamino aligoethylene sulfide Example 28 wasrepeated using N-methylbenzylamine instead of benzylamine. The oligomerwas an oil with the structure One-half mole of ethylenemonothiolcarbonate and one-half mole of diethylamine were stirredtogether for 1 hour in a mixture of 200 ml. of water plus 200 ml. 9fmethanol. The white oligomer was washed and dried. It contained nocarbonyl and its structure is z s 2 z z 11 A second experiment identicalin all respects except that the ethylenemonothiolcarbonate was addeddropwise had an identical infrared spectrum.

Example 31.-Di-n-burylamina-o ligaethylene sulfide One-tenth mole ofdi-n-butylamine and 0.1 mole ethylene monothiolcar-bonate were refluxedtogether for 5 hours in ml. of a 1:1 mixture of methanol and water. Thewhite oligomer contained no carbonyl. The structure was shown to be (n-CH N(CH CH S) H.

Example 32.-Di-sec.buty lamina-aligoethylene sulfide This was identicalto Example 31 excepting that disec.butylamino was used instead ofdi-nbutylamine. There was no carbonyl band in the infrared. Thestructure was Example 33.M0rp0h0'lin0carbonyloxy-oligoethylene sulfideOne-half mole of ethylene monothiolcarbonate plus 1.5 mole of morpholinewas refluxed for six hours in a mixture of 500 ml. of water plus 500 m1.of methanol. The-re was little solid present at this stage. The reactionmix ture was distilled through a 14" Vigreux column. After removal ofsolvents and excess morpholine, 33 g. product was obtained. It was shownby infrared and elemental analysis to be The molecular weight was 286.

Example 35.-n-Decylcarbamoyloxy-oligoethylene sulfide One-tenth mole ofn-decylamine and 0.1 mole of ethylene monothiolcarbonate were reacted in200 ml. of a 1:1 mixture of methanol and water. The ethylenemonothiolcarbonate was added dropwise over a 20 minute period. Themolecular weight was 1135 by iodometric titration in dimethylformamide.The structure is Example 36.Prpylcarbamoyloxy-olgioethylene sulfideOne-tenth mole of ethylene monothiolcarbonate and 0.1 mole ofpropylamine were refluxed together for five hours in a mixture of 75 ml.of methanol and 75 ml. of water. The white oligomer was washed withwater and dried. A strong carbonyl band was exhibited at about 5.95microns. The structure was shownto be One-half mole of ethylenemonothiolcarbonate was stirred into a mixture of 200 ml. of aqueous NaOHplus 200 ml. of dioxane. After 2 hours the oligomer was separated andwashed. The product contained no carbonyl group. Its structure was HO(CHCH S) ,H.

From a similar run in which the ethylene monothiolcarbonate was addeddropwise over a one-hour period an oligomer of similar structure wasobtained. An iodometric titration indicated a molecular weight of 369.

Example 38.-Ethoxy-oligoethylene sulfide 0.5 moles of ethylenemonothiolcarbonate was added dropwise over a period of 1 hour to 6 g. ofsodium dissolved in 800 m1. of ethanol. An oligomer having the structureC H O(CH CH S), H separated immediately.

Example 39.2-(eth0xyeth0xy)ethoucyoligoethylene sulfide Six grams ofsodium was dissolved in 500 ml. of 2- (ethoxyethoxy)ethanol. Thissolution was heated on a steam bath and 0.5 moles of ethylenemonothiolcarbonate was added dropwise. The oligomer which formed had nocarbonyl in its infrared spectrum and has the following structure IC2H5OC2H4OC2H4O(CH2CH2S H- Example 40.-n-Decylmereapto-oligo'ethylenesulfide Six grams of sodium was dissolved in a mixture of 300 -ml. ofethanol and 0.25 moles of l-n-decanethiol. This solution was refluxedand 0.5 moles of ethylene monothiolcarbonate was added over a period of1 hour. The oligomer showed no carbonyl band in the infrared spectrum.It has the structure n-C l-I -S(CH CH S) H.

Example 4] .Benzylmercaptoligoefhylene sulfide This preparation wassimilar to that described in Example 40 except benzenemethanethiol wasused instead of l-n-decanethiol. The oligomer contained no carbonyl andhas the structure C H CH S(CH CH S) H.

Exalmple 42..Phenylmercapto-oligoethylene sulfide This preparation wassimilar to that disclosed in Example 40 except that thiophenol was usedinstead of 1- n-decanethiol. The oligomer had the structure 10 Example43.--Phen.oxy-0ligoezhylene sulfide Ten grams of phenol containing 0.25gm. of sodium was warmed until the sodium dissolved. One hundred ml. ofdioxane and 10.4 g. of ethylene monothiolcarbonate was added. Thesolution was refluxed for 5 hrs. The oligomer was a low molecular weightoil.

Example 44.Did0decylamino-oligoethylene sulfide One-tenth mole ofdidodecylamine was refluxed for 5 hrs. in ml. of methanol containing 0.2moles of ethylene monothiolcarbonate. A low molecular weight oil of thestructure C H N*(CH CH S),,=H was obtained.

Example 45 .-M ercapto-oligoethylene sulfide Example46.1,I-dim'ethylhydrazinobis-oligoethylene sulfide To a refluxingsolution of 1,1-dimethylhydrazine (180.3 g., 3.0 mole) was added 104g.(1.0 mole) ethylene monothiolcarbonate dropwise in 1 hour. A vigorousreaction ensued precipitating 50 g. of white powder which had amolecular weight 6 68 for a secondary amine with one oligoethylenesulfide chain. Elemental analysis and infrared spectroscopy (absence ofthe 2.9 micron band for secondary amine) indicates that the product isthe his- (oligoethylene sulfide) with the average chain length of 10units.

Calc. for C H N S C, 40.4; H, 7.5; N, 2.1; S, 49.8. Found: C, 40.4; H,7.1; N, 1.8; S, 50.1.

Example 47 .Beuzyl0xy-oligoethylene sulfide ml. diethylether g. whitepowdery solid precipitated with a molecular weight of 606 or thebenzylether with 8.3 repeating ethylene sulfide units.

Example 4 8.tert.0cladecy lamina-oligoethylene sulfide Ten grams oftert.octadecylamine and 500 ml. methanol were vigorously refluxed on asteam bath while 104 g. 1.0 mole) ethylene monothiolcarbonate was addedin one portion. The clear solution was refluxed 24 hours and uponconcentration a white powder separated having a molecular weight of 901or 9.6 repeative ethylene sulfide units.

The invention has been described in considerable detail with particularreference to preferred embodiments thereof, but it will be understoodthat variations and modifications can be effected within the spirit andscope of the invention as described hereinabove and as defined in theappended claims.

We claim:

1. A process for preparing a compound having the formula wherein r is aninteger of from 1 through 2, R is selected from the group consisting ofhydrogen, hydroxymethyl, and alkyl of from 1 through 8 carbon atoms, nis an integer of from 2 through 20, and X is wherein, when r is 2, G isselected from the group consisting of and and RRNN=, wherein Y isselected from the group consisting of hydrogen and R, and x is aninteger of from 2 through 18, (b) H N- HO- (d) RS, and (e) RO, whereinin (a), (d), and (e), R is selected from the group consisting of alkylof from 1 through 18 carbon atoms, cyclohexyl, cyclopentyl, benzyl, andphenyl, which process comprises reacting, in a mercaptide ionenhancingmedium, (I) a sulfide selected from the group consisting of Q-CO--ACHCHR'BH and UHF-CHE i t II 0 wherein Q is alkoxy of from 1 through 18carbon atoms, A and B are dissimilar and are selected from the groupconsisting of sulfur and oxygen, and R is selected from the groupconsisting of hydrogen, hydroxymethyl, and alkyl of from 1 through 8carbon atoms and (II) a nucleophilic initiating agent selected from thegroup consisting of I (i) XH wherein X is selected from the groupconsisting of. RHN, RRN,

r r HN (CH2) ,N-H

wherein Y is selected from the group consisting of hydrogen and R asabove defined, (iii) wherein Y is selected from the group consisting ofhydrogen and R as above defined,

(iv) RRN-NH wherein R is as above defined, and

(v) XM wherein X is selected from the group consisting of RO, and RS-wherein R is as above defined and M is an alkali metal.

2. A process according to claim 1 in which the mercaptide ion-enhancingmedium is a solvent which induces ionization.

3. A process according to claim 1 in which the starting material isethyl Z-mercaptoethylcarbonate.

4. A process according to claim 1 in which the starting material isethylene monothiolcarbonate.

5. A process according to claim 1 in which the starting material isethyl 2-hydroxyethylthiolcarbonate.

6. Process for preparing 1,1(dihydroxymethyl)ethylamino-oligoethylenesulfide which comprises reacting Z-amino-Z-methyl-1,3-propanediol andethyl-Z-mercaptoe-thylcarbonate.

7. Process of preparing tris(hydroxymethyl)methylaminooligoethylenesulfide which comprises reacting 2-amino 2 hydroxymethyl 1,3 propanedioland ethyl 2-mercaptoethylcarbonate.

8. Process of preparing 2-hydroxyethylaminooligoethylene sulfide whichcomprises reacting 2-aminoethanol and ethyl Z-mercaptoethylcarbonate.

9. Process of preparing 1,1-dimethylhydrazinobisoligoethylene sulfidewhich comprises reacting 1,1-dimethylhydrazine and ethylenemonothiolcarbonate.

References Cited UNITED STATES PATENTS 9/1948 Carlson 260-327 1/1963Johnson et al. 260-327 CHARLES B. PARKER, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,326,977 June 20 1967 Dee L. Johnson et al.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below. Y

Y Column 1, lines 44 and 45, after "-N(CH N-" insert column 3, lines 26and 27, for "ethonolamine" read ethanolamine column 4, line 14, for "(SHCH S)" read (CH CH S) column 8 line 54 for "sec butylamino" read H sec.butylamine lines 72 to 74, the formula should appear as shown belowinstead of as in the patent:

column 9 line 62 for "nC H S(CH CH S) l-l" read r 1 C H S[CH CH H column10, line 22, for

"separated." read separated, column 11, line 46, for "RRN" read RRN-Signed and sealed this 22nd day of October 1968.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissionerof Patents

1. A PROCESS FOR PREPARING A COMPOUND HAVING THE FORMULA